(Cont.) 3. The sulfonimido ligand is bound in a K2-N, O chelate. This complex is a proficient nitrene transfer reagent to carbon monoxide, phosphines, and ethyl vinyl ether. A rhodium(lll) hydride chloride complex containing two N-heterocyclic carbene ligands, one of which is cyclometallated, is a convenient synthetic equivalent of a rhodium(l) chloride complex. Treatment of the rhodium(Ill) hydride with acetonitrile results in reductive elimination to form a rhodium(l) chloride complex. The chloride is readily abstracted by sodium azide to form a cationic rhodium(l) complex coordinated by two molecules of acetonitrile and containing an unbound azide. Upon exposure to UV light, this molecule undergoes cyclometallation to form a cationic rhodium(lll) hydride complex. The rhodium(lll) hydride chloride complex can be treated with oxygen to form a rhodium(lll) peroxide complex. The neutral peroxide complex has poor reactivity with trimethylphosphite and t-stilbene. However, a cationic rhodium peroxide complex oxidizes trimethylphosphite and t-stilbene at elevated temperatures.

Abstract The ubiquitousness of amines in pharmaceuticals, agrochemicals, ligands for transition metals, biologically active natural compounds and functional materials is the strong motivation of organic chemists to develop highly efficient yet mild reactions to install valuable C-N bonds. Transition metal-catalyzed nitrene transfer is a convenient strategy to directly functionalize a hydrocarbon substrate with amine functionality. For all means of C(sp3)−H amination, one of the core issues hampering their developments is the difficulty to differentiate multiple C-H bonds that have nearly identical electronic properties and bond strengths. As described in this work, this problem is addressed through utilizing Ag catalysts based on deliberately designed ligands, which is inspired by mechanism study, to achieve tunable site-, regio-, and stereoselectivity. Chapter 1 gives a brief introduction by providing a selected review of literature on transition metal-catalyzed C(sp3)−H aminations reactions via nitrene transfer, emphasizing the common problems associated with reactivity and selectivity. Chapter 2 demonstrates both the solid and solution-state behavior of diverse Ag(I) catalysts competent for nitrene transfor through X-ray characterization and NMR studies, and discusses our understanding of how the ligand identity manipulate those behavior of corresponding Ag(I) complexes. Chapter 3 describes both computational models and experimental probes revealing possible roles of noncovalent interactions in directing the site-selectivity of silver-catalyzed C−H aminations. Chapter 4 addresses the fluxional behavior of Ag(tpa)OTf in solution potentially hampering its site-selectivity in nitrene insertion by a rigid ligand. Finally, chapter 5 provide a novel silver catalytic system which is able to tune the selectivity between [beta] or [gamma] C-H bond amindation of an easily prepared carbamate, overriding substrate control, and amidate traditionally difficult primary aliphatic C-H bonds. Further experimental and computational studies revealed some mechanistic insights into this system. Additional, synthetic utility of this methodology was proven by the late-stage functionalization of natural products and drug-like molecules, even in gram-scale.

This dissertation, "Oxidation and Nitrene Transfer Reactions Catalyzed by Iron-oligopyridine Complexes" by Peng, Liu, 劉鵬, was obtained from The University of Hong Kong (Pokfulam, Hong Kong) and is being sold pursuant to Creative Commons: Attribution 3.0 Hong Kong License. The content of this dissertation has not been altered in any way. We have altered the formatting in order to facilitate the ease of printing and reading of the dissertation. All rights not granted by the above license are retained by the author. DOI: 10.5353/th_b4266427 Subjects: Oxidation Nitrenes - Reactivity Pyridine Metal complexes Metal catalysts

Advances in Heterocyclic Chemistry, Volume 142, the latest release in this definitive series, combines descriptive synthetic chemistry and mechanistic insight to yield an understanding of how chemistry drives the preparation and useful properties of heterocyclic compounds. Chapters in this new release include Recent advances in the Synthesis of Benzo[b]furans, Recent Advances in the Synthesis of 6-Membered Heterocycles via Domino and Multicomponent Reactions (from 2017-2022), Multi-component synthesis of isatin based bioactive heterocycles, Recent advances in the chemistry of pyrazolo[1,5-a]pyrimidines, The Literature of Heterocyclic Chemistry, Part XXI, 2021, and much more.Additional sections present the latest Advances in applications of dihydropyridines in organic chemistry and Strategies for the annulation of five-membered sulfur-nitrogen rings to benzene and heterocycles. - Considered the definitive serial in the field of heterocyclic chemistry - Serves as the go-to reference for organic chemists, polymer chemists, and many biological scientists - Provides the latest comprehensive reviews written by established authorities in the field - Combines descriptive synthetic chemistry and mechanistic insights to enhance understanding on how chemistry drives the preparation and useful properties of heterocyclic compounds